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Effect of ligand substituents and tuning the spin-state switching in manganese(iii) complexes

Ghosh, S and Bagchi, S and Kamilya, S and Mondal, A (2021) Effect of ligand substituents and tuning the spin-state switching in manganese(iii) complexes. In: Dalton Transactions, 50 (13). pp. 4634-4642.

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Official URL: https://doi.org/10.1039/d1dt00284h


Three mononuclear manganese(iii) complexes based on flexible hexadentate ligands obtained from the condensation ofN,N′-bis(3-aminopropyl)ethylenediamine and salicylaldehyde or salicylaldehyde with substitutions at the 5 or 3,5 positions, namely [Mn(X-sal2-323)](BPh4) (X = 5 H,1; X = 5 Br,2, and X = 3,5 Br,3) have been synthesized. The impact of ligand substituents has been studied by variable temperature single-crystal X-ray diffraction analyses, and magnetic, spectroscopic and electrochemical investigations. The complexes have an analogous monocationic MnN4O2surrounding offered by the flexible hexadentate ligand in a distorted octahedral geometry. Complex1remains in the high spin state over the entire temperature range, while complex2shows a reversible and complete two-step thermo-induced spin-state switching. An incomplete spin-state switching from a high spin to an intermediate high-spin low-spin (1 : 1) state was observed for complex3. Single-crystal X-ray structural studies show the presence of three different spin states in2during the occurrence of the spin-state switching process. Electrochemical investigations showed that the reduced state of manganese(iii) centers in3is easily accessible in comparison to complexes1and2. © The Royal Society of Chemistry 2021.

Item Type: Journal Article
Publication: Dalton Transactions
Publisher: Royal Society of Chemistry
Additional Information: The copyright for this article belongs to Royal Society of Chemistry.
Keywords: Ligands; Single crystals; Spin dynamics; Switching; Synthesis (chemical); X ray diffraction analysis, Electrochemical investigations; Ligand substituents; Manganese complex(III); Octahedral geometry; Single crystal X-ray diffraction analysis; Single-crystal x-ray structural study; Spin-state switching; Variable temperature, Manganese compounds
Department/Centre: Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited: 22 Feb 2023 03:31
Last Modified: 22 Feb 2023 03:31
URI: https://eprints.iisc.ac.in/id/eprint/80427

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